A preferable molecular crystal membrane for H 2 gas separation

Transcription

1 Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 2014 Supporting information A preferable molecular crystal membrane for H 2 gas separation Yuichi Takasaki, Satoshi Takamizawa* Department of Nanosystem Science; Graduate School of Nanobioscience; Yokohama City University; 22-2 Seto; Kanazawa-ku, Yokohama, Kanagawa ; Japan staka@yokohama-cu.ac.jp

2 (a) Experimental information (Preparation of crystal) Introducing pyrazine vapor (0.20 g, 2.5 mmol) into the methanol solution (200 ml) of copper(ii) acetate monohydrate (0.208 g, 1.04 mmol) and 9-anthracenecarboxylic acid (0.449 g, 2.02 mmol) gave dark red, rod-like single crystals of 1 with a size of m in 16.4% yield (.3 mg). Well-formed single crystals were used for experiments after being vacuum dried at 298 K. (Preparation of single-crystal membrane) A single crystal of 1 was set in a hole of an aluminum sheet and the gap between the oriented crystal and the aluminum plate was sealed with epoxy resin. The single crystal was used as a membrane with the area of the crystal surface as mm 2 for (001) and a crystal thickness of mm along [001]. For the crystal membrane, the single crystals were cut to a suitable size along each crystal face. (X-ray single crystal diffraction analysis) Single-crystal X-ray structural analysis of 1 was performed at K on a Bruker Smart APEX CCD area diffractometer (Bruker AXS K.K.) with a nitrogen-flow temperature controller using graphite-monochromated Mo K radiation ( = Å). Empirical absorption corrections were applied using the SADABS program. The structure was solved by direct methods (SHELXS-97) and refined by full-matrix least-squares calculations on F 2 (SHELXL-97) using the SHELX-TL program package. Non-hydrogen atoms were refined anisotropically; hydrogen atoms were fixed at calculated positions by riding model approximation. (Gas adsorption measurement) Gas adsorption measurements were performed at 293 K on a Belsorp-HP Measurement System (BEL JAPAN, Inc.) after drying the microcrystalline sample of 1 (412.7 mg) at 353 K for 2 hours. (Adsorbate gases: H 2, N 2, Ar, O 2, CO, CH 4, and CO 2 ) (Gas permeation measurement) Gas permeation was performed along the direction of [001] by using the single-crystal membrane on GTR-20XAYU Analyzer (GTR Tech Corporation) by the differential pressure method at 293 K and a differential pressure of 150 kpa. Gas permeation was monitored by gas chromatography with a thermal conductivity detector (TCD) on a GC-2014 Gas Chromatograph (Shimadzu Corporation). Pages S1

3 (b) Crystallographic data and ortep drawing of 1 Table S1. Crystallographic data of 1. Dimension / mm Empirical formula C 64 H 40 Cu 2 N 2 O 8 M / g mol Crystal system Tetragonal Space group P4/nnc T / K a / Å (2) b / Å (2) c / Å 9.584(2) / / / V / Å (8) Z 2 D calcd / Mg m (Mo K ) / mm Independent reflections (R int ) 1178 (0.1282) Goodness-of-fit on F R 1 (I > 2 (all data)) (0.0806) wr 2 (I > 2 (all data)) (0.1493) Largest diff. peak (hole) / e Å (-1.207) Figure S1. Molecular structure of 1 as an ortep view at 50% probability level for the ellipsoid. Pages S2

4 (c) Gas adsorption properties of 1 at room temperature In gas adsorption measurement, the linear isotherm only for H 2 and normal type I isotherms for other gases (O 2, Ar, N 2, CH 4, and CO 2 ) were obtained at 293 K. The specific surface area calculated from N 2 gas isotherm is m 2 g -1 which is near the value of 2 (211.8 m 2 g -1 ). These adsorption isotherms indicate that the all gas species other than H 2 were sufficiently adsorbed in the channel of 1 at 293K and 150 kpa. Figure S2. Gas adsorption isotherm of 1 for H 2 (diamond), O 2 (circle), Ar (x), CO (plus), CH 4 (inverted triangle), N 2 (triangle), and CO 2 (square) at 293 K. Table S2. Gas adsorption amount (A) and gas concentration (C) in the channel at 293 K and 150 kpa calculated from the adsorption amount at a crystal density ( K) of g cm -3 for 1. Gas concentration for helium was substituted with that for hydrogen because the adsorption measurement for helium gas was not performed. A C Gas / Ncc g -1 / mol m -3 H O Ar CO CH N CO Pages S3

5 (d) Estimation of permeability based on Knudsen diffusion model Table S3. Estimated permeability for 1 at 293 K and 150 kpa based on Knudsen diffusion model. P dmin and P dmax are the estimated permeability based on the values of d min (= 6.2 Å) and d max (= 7.9 Å) in Knudsen diffusion model, respectively. Gas P dmin / mol m m -2 s -1 Pa -1 P dmin / Barrer P dmax / mol m m -2 s -1 Pa -1 P dmax / Barrer He H O Ar CO CH N CO (1 Barrer = mol m m -2 s -1 Pa -1 ) Pages S4

6 (e) Comparison of H 2 selectivity and permeability Table S4. Ideal selectivity (F (ratio of permeability)) of H 2 versus other gas species and H 2 permeability (P H2 ) for reported membranes which were shown in Fig. 3(a-c). Membrane Gas F P H2 / Barrer Reference 1 CO This work CH N [Cu 2 (bza) 4 (pyz)] n CO S1 CH N 2 10 Polyethylene CO S2 Cobalt doped silica CO 4.5 S3 Molecular sieve carbon CO S4 CO Polyimide (PI-2080) CO S5 Polyimide Matrimid 5218 CO S6 N Molecular sieve silica CO S7 Titania CO S8 N MFI-Type Zeolite CO S9 Polysulfone CH S10 Defect free silica CH S11 N 2 64 Poly(tert-butyl acrylate) CH S12 PIM-EA-TB CH S13 N Teflon CH S14 HKUST-1 (Cu-BTC) CH S15 (1 Barrer = mol m m -2 s -1 Pa -1 ) N 2 22 CH S16 N CH S17 N Pages S5

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